A Study on the Electrochemical and Electrochemiluminescent Behavior of Homogentisic Acid at Carbon Electrodes

The electrochemical oxidation and electrochemiluminescent behavior of homogentisic acid (HGA) has been studied in aqueous solutions over a wide pH range by linear sweep voltammetry, cyclic voltammetry, chronocoulometry at a glassy carbon electrode, by controlled potential electrolysis at a large area spectroscopic graphite electrode, and by spectroelectrochemistry at an optically transparent drilled holes graphite (DHG) electrode in a thin‐layer cell. The studies reveal that the electrochemical oxidation of HGA at carbon electrodes is a reversible process involving two‐electron, two‐proton transfer. In addition to the electrochemical oxidation, the chemical oxidation of HGA by dissolved oxygen was investigated by spectroscopic method combined with voltammetry. It was revealed that HGA is fairly stable in strongly acidic media but readily oxidized by dissolved oxygen in alkaline media giving rise to 1,4‐benzoquinone‐2‐acetic acid, the same product as that of electrooxidation of HGA. This oxidation product is stable in acidic, neutral and weakly alkaline media, but can further degrade in strongly alkaline media yielding oxalate as the final product. The electrochemiluminescent mechanism of HGA in the presence of Ru(bpy)₃²⁺ at a glassy carbon electrode was also investigated in detail, based on which a sensitive ECL method for determination of HGA was developed, and the detection limit was 3.0×10^?8 mol L^?1.     

Detection of Cadmium and Copper Cations Using Amorphous Nitrogenated Carbon Thin Film Electrodes

Nitrogenous amorphous carbon (a‐CN_x) thin films were deposited by radio‐frequency cathodic magnetron sputtering (13.56 MHz) on polished and etched titanium disks. While these films are cheaper to prepare than commonly reported carbon‐based electrodes, the usable electrochemical window in aqueous solution is within the same range and spans from ?1.5 to +1.8 V vs. SCE. The electrochemical reactivity was tested using the ferri‐ferrocyanide redox couple as a function of the thin films preparation parameters. The obtained electrochemical properties allow the use of these a‐CN_x thin films for stripping electroanalysis of cations in water, minimizing potential solvent reactivity. Cadmium and copper were used to test these detection abilities. Better analytical properties (notably sensitivity and linearity) were obtained as compared to a commercial boron doped diamond electrode. Preliminary competition/interaction experiments for these two cations were performed.     

碱性鲁米诺体系在玻碳和铂电极上的电位分辨电致化学发光研究

提出一种使用循环伏安（ＣＶ）扫描电位下的电致化学发光（ＥＣＬ）研究方法,在自制的仪器系统中同时进行ｉ－Ｅ和Ｉ－Ｅ测量,获得对应的ＣＶ和电位分辨的电致化学发光（ＰＲＥＣＬ）曲线。首先发现碱性鲁米诺体系在玻碳电极（ＧＣＥ）上呈现２个阳极发光峰（在０．３２Ｖ、０．３９Ｖｖｓ．Ａｇ）和１个阴极发光峰（在－０．６２Ｖ）,在Ｐｔ电极上呈现２个阳极发光峰（在０．４９Ｖ、０．７５Ｖ）。结合ＣＶ、一阶微分伏安、Ｃｌ     

Influence of Phosphorus Doping Level and Acid Pretreatment on the Voltammetric Behavior of Phosphorus Incorporated Tetrahedral Amorphous Carbon Film Electrodes

Phosphorus incorporated tetrahedral amorphous carbon (ta‐C:P) films are prepared by filtered cathodic vacuum arc technology with phosphine as the dopant. The influence of phosphorus doping level and acid pretreatment on the electrochemical properties of ta‐C:P electrodes is investigated by cyclic voltammetry, Raman spectroscopy and X‐ray photoemission spectroscopy. Results indicate that phosphorus incorporation improves the electrical and electrochemical behaviors of the films. A moderate phosphorus atomic fraction facilitates the interfacial electron transport in context of a high content of effective phosphorus impurities. Furthermore, acid pretreatment activates the surface of the films and gives an excellent reversible feature towards ferricyanide oxidation reaction by removing the inactive oxygenated sites and exposing the active conduction channels.     

电化学石英晶体微天平研究高氯酸钠水溶液中活性炭电极的离子存储行为

以电化学石英晶体微天平(EQCM)为主要测试手段,在不同浓度的高氯酸钠(NaClO4)水溶液中研究了水合离子吸附到活性炭电极孔隙过程中电极的质量变化.对于每种电解液,根据Raman光谱和EQCM数据分别计算了本体溶液中和电极/溶液界面上Na+的水合数.通过比对这两组Na+水合数,探讨了Na+存储到活性炭负极过程中的去溶剂化效应.     

Electrochemical Reduction of S(IV) Compounds in Water‐Ethanol Solutions at Nafion/Tetraruthenated Porphyrins Glassy Carbon Modified Electrodes

This work describes electrocatalytic detection of S(IV) compounds in water‐ethanol solutions under acidic conditions, on a glassy carbon electrode modified with Co(II) tetraruthenated porphyrin electrostatically assembled onto a Nafion film. The I_pc current shows a linear relationship with the concentration of S(IV) oxo‐anions. Controlled potential electrolysis shows that thiosulfate was detected as reaction product. Rotating disk electrode and UV‐visible spectroelectrochemistry experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film and the formation of an intermediary between Co center and S(IV) species. The reproducibility of the modification methodology presents a RSD of 4.1%.     

Electrochemical Characterization of Poly(N‐acetylaniline)/Nafion Composite Film in Neutral and Basic Aqueous Solutions

Electrochemical synthesis of poly(N‐acetylaniline) (PNAANI)/Nafion composite film was carried out by cyclic voltammetry (CV). Its surface morphology, which was evaluated by scanning electron microscopy (SEM), revealed that PNAANI was dispersed into the Nafion film uniformly. X‐ray photoelectron spectrum (XPS) of the composite film was also examined. The electroactivity of the composite film was high in neutral and basic solutions, and the stability of PNAANI/Nafion film in neutral and basic solutions was excellent.     

Voltammetric Determination of 5‐Aminoquinoline at Carbon Film Electrode and Carbon and Gold Screen Printed Electrodes – A Comparative Study

Aminoquinolines are widely used as antimalarial drugs and thus there is an ever increasing demand for their determination. In this paper, non‐traditional carbon film electrode developed in our laboratory (CFE) with easily replaceable carbon film was used for the determination of 5‐aminoquinoline (5‐AQ) and compared with well‐established commercially available carbon screen printed electrode (CSPE) and gold screen printed electrode (AuSPE). Electrochemical behavior of 5‐AQ was characterized by cyclic and differential pulse voltammetry. Differences in electrochemical behavior of 5‐AQ at different electrodes were evaluated. Determination of 5‐AQ was carried out by differential pulse, square wave, and direct current voltammetry. Practical applicability of the method was verified by direct determination of 5‐AQ in model samples of drinking and river water. Achieved limits of quantitation were in submicromolar concentrations. It was found out that novel CFE in terms of overall performance is in most aspects superior to routinely used commercially available CSPE and AuSPE.     

Electrochemical Behaviors of Baicalin at an Electrochemically Activated Glassy Carbon Electrode and Its Determination in Human Blood Serum

Electrochemical behavior of baicalin (BA) at an electrochemically activated glassy carbon electrode (GCE) had been investigated in Britton‐Robinson (B‐R) buffer solution (pH = 2.87) by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the electrode exhibited an electrocatalytic activity toward the redox of BA. The electron transfer coefficient (α) and the standard rate constant (k_s) of BA at the electrochemically activated glassy carbon electrode were calculated. The reaction mechanism was proposed and discussed in this work. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of BA in the range of 5.0 × 10^?8 to 3.0 × 10^?6 mol L^?1 (r = 0.9990), with a detection limit of 2.0 × 10^?8 mol L^?1. The relative standard deviation (R.S.D.) for five times successful determination of 1.0 × 10^?6 mol L^?1 baicalin were 2.9%. The proposed method was also successfully applied for the determination of BA in human blood serum.     

Determination of Hg2+ in Tap Water Based on the Electrochemiluminescence of Ru(phen)32+ and Thymine at Bare and Graphene Oxide‐Modified Glassy Carbon Electrodes

The electrochemiluminescence (ECL) of the Ru(phen)₃²⁺/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg²⁺ in tap water. The ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)₃²⁺/T system rapidly decreased with the addition of Hg²⁺ because of the formation of a T‐Hg²⁺‐T complex. A linear response (R²=0.9914) was obtained over a Hg²⁺ concentration range of 1.0×10^?9 mol/L to 1.0×10^?5 mol/L with a detection limit of 3.4×10^?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10^?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg²⁺ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg²⁺.